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| United States Patent |
5,260,459
|
|
Brunke
, et al.
|
November 9, 1993
|
Cyclic isolongifolanone-ketals - their manufacture and their application
Abstract
The cyclic Isolongifolanone ketals of the general formula A wherein the
wavy lines mean .alpha. and .beta.-configuration and R,R' mean radicals of
hydrogen, methyl or ethyl, are new. With preference they are used either
as odorants or as components of perfume compositions. They are
manufactured from Isolongifolene which is itself produced from Longifolene
as is well known. Isolongifolene is oxydized to Isolongifolene-3-on and
this is reacted with aliphatic 1,2-diols in apolar solvents with the
separation of water.
| Inventors:
|
Brunke; Ernst-Joachim (Pippingsbusch 3, Holzmimden, 3450, DE);
Schatkowski; Dietmar (Weststrasse 7, Stadtoldendorf 3457, DE)
|
| Appl. No.:
|
978239 |
| Filed:
|
November 18, 1992 |
Foreign Application Priority Data
| Current U.S. Class: |
549/336 |
| Intern'l Class: |
C07D 317/92 |
| Field of Search: |
549/336
|
References Cited
U.S. Patent Documents
| 3887622 | Jun., 1975 | Boelens et al.
| |
| 4331569 | May., 1982 | Inoue et al. | 549/336.
|
| 4774225 | Jul., 1988 | Giraudi | 549/336.
|
| 4841075 | Jun., 1989 | Matsushita et al. | 549/336.
|
| Foreign Patent Documents |
| 2336798 | Jan., 1974 | DE.
| |
| 1505821 | Mar., 1978 | GB.
| |
Other References
CA 81(5): 25442f (1974).
CA 89(7): 59977g (1978).
|
Primary Examiner: Cintins; Marianne M.
Assistant Examiner: Peabody; John
Attorney, Agent or Firm: Dominik, Stein, Saccocio, Reese, Colitz & Van der Wall
Claims
We claim:
1. Cyclic isolongifolanone ketals of the general formula (A) wherein the
wavy lines mean .alpha.- and .beta.- configuration and R and R'
independently mean radicals selected from the group consisting of
hydrogen, methyl or ethyl
##STR3##
2. Cyclic isolongifolanone ketals as in claim 1, wherein R and R' represent
hydrogen.
3. Cyclic isolongifolanone ketals as in claim 1, wherein R represents
hydrogen and R' represents methyl, or R represents methyl and R'
represents hydrogen.
4. Cyclic isolongifolanone ketals as in claim 1, wherein R represents
hydrogen and R' represents ethyl, or R represents ethyl and R' represents
hydrogen.
5. Cyclic isolongifolanone ketals as in claim 1, wherein R and R' represent
methyl (.alpha.,.beta.).
6. Cyclic isolongifolanone ketals as in claim 1, wherein said ketals are
produced by the process comprising obtaining isolongifolene from
longifolene, oxidizing isolongifolene to isolongifolene-3-one and reacting
with aliphatic 1,2-dioles in an apolar solvent accompanied by separation
of water.
Description
Today, industrially manufactured perfume oils consist of synthetic odorants
largely. The traditional application of essential oils or extracts of
vegetable or animal origin is now mainly restricted to the area of
alcoholic perfumery. Perfume for detergents, soaps, household cleaners and
similar products requires the use of odorants which meet the technical
demands of stability and substantivity. To comply with these demands,
perfumes which are used in technical consumer products are essentially
composed of synthetic odorants. Because these perfume oils are needed in
large quantities as a result all major perfume companies and manufacturers
of aroma chemicals have dedicated their research work over the last
decades to produce new aroma chemicals.
It has become increasingly apparent during the last 10 years that synthetic
odorants which were originally destined for the technical perfumery, and
which due to their low prices and high stability were accordingly
positioned in the market are now more and more used in the alcoholic
perfumery. Perfumers have used their perfumistic know-how gained from the
use of synthetic aroma chemicals in technical perfumes and applied it also
to alcoholic perfumery as aesthetic chances may allow. Today, a sucessfull
new aroma chemical has to meet the following demands:
1. it has to present a high olfactory and aesthetic value and must be
applicable in as wide a range of fragrance products as possible;
2. it has to be stable in most technical applications;
3. it has to show a good value-/for money-ratio;
4. it should be manufactured from generally available raw materials from
renewable resources, whenever possible.
Such a raw material of natural origin available in large quantities is
Longifolene (1) which is to be found as a main component in the Indian oil
of turpentine and as a minor component in many other turpentine oils and
other essential oils.
About 20 years ago, research laboratories of the aroma chemical industry
produced a number of derivative products from Longifolene, which had
odorant qualities. As reported in a summary by G. Ohloff in his book
"Riechstoffe und Geruchssinn" (Springer-Verlag, Berlin, 1990, ISBN-Nr.
3-540-52560-2, pages 87-88) at least 4 commercial odorants are derived
from the Longifolene (1). The Isolongifolene (2) which is obtained by the
isomerization of Longifolene (1) can be proved to have fathered 13
commercial products. The chemistry and olfactory qualities of derivates of
the Isolongifolene (2) are summarized by G. Farber and H. Tan:
"Riechstoffe aus Isolongifolen", G. Farber, Parfumerie & Kosmetik, 68, 18
(1987)
"Der Gebrauch von Riechstoffen aus Isolongifolenen in der Parfumerie", H.
Tan, Parfumerie & Kosmetik, 67, 564 (1986)
The derivates of Isolongifolene (2) obtained by epoxidation, Prins-reaction
(reaction with formaldehyde) or allylic oxidation are considered
olfactorily more valueable than the derivates of Longifolene (1). They (2)
are odorants of a warm-woody odor type, with some little amberlike aspects
(Ohloff loc. cit.).
The epoxide (3) obtained by the reaction of Isolongifolene with peracids
can be transferred as is known into mixtures of epimer ketones. The ketone
mixtures may contain different proportions of isomers with different odor
effects. The ketone 4a is preferably manufactured in kinetic reaction
while the ketone 4b is the thermodynamically more stable epimer.
According to the state of the art as described above, this area of the
aroma chemical chemistry is considered to be especially well researched.
Together with the derivates of Longifolene and Isolongifolene which have
useful odor qualities, a large number of other derivates are known with
little or no such value.
##STR1##
It is all the more surprising therefore, that new valuable odorants could
be found in the area of the Longifolene derivates such as the herewith
claimed new cyclic acetals of the general formula A. The acetals of the
general formula A present unique olfactory qualities clearly standing out
from the known odorants derivated from Isolongifolene (2) and superior to
them. The new compounds of the general formula A present strongly woody
olfactory qualities with flowery-fresh effects and with a velvety
moss/ambra accent (see example 1); they are especially longlasting and act
as fixatives.
For the manufacture of compounds of the general formula A, Longifolene (1)
has been treated as is well known with a mixture of acetic acid and
sulphuric acid [U. R. Nayak, S. Dev, Tetrahedron 8, 42-48 (1960)] or with
bortrifluorid-etherate [R. E. Beyler, G. Ourisson, J.Org.Chem. 30,
2838-2839 (1965)] to obtain Isolongifolene (2) by isomerization. The
epoxide (3) [L. K. Lala, J. B. Hall, J.Org.Chem. 35, 1172, (1970); J. R.
Prahlad, R. Ranganathan, W. Ramdas Nayak, T. S. Santhanakrishnan, S. Dev,
Tetrahedron Lett. 8, 417 (1964)] obtained by epoxidation of Isolongifolene
(2) has been transformed, as is well known, into the mixture of the epimer
ketones 4a/4b [R. Ranganathan, U. R. Nayak, T. S. Santhanakrishnan, S.
Dev, Tetrahedron 26, 621 (1970)]. In known conditions of the kinetic
reaction the ring-opening of the epoxide produced a mixture of ketones
4a/4b concentrated in 4a (see example 2=96:4). It is known that 4a will be
isomerized into the thermodynamically more stable ketone 4b under the
influence of basic catalysts or by heating. Depending on the conditions of
the reaction, mixtures of equilibrium of 4a/4b are obtained [L. K. Lala,
J. Org. Chem. 36, 2560-2561 (1971)].
Our example 3 shows an isomerization not yet described to date leading from
a mixture of ketones 4a/4b (96:4) to a specially highly concentrated
mixture of equilibrium 4a/4b (9:91). The ketones 4a/4b have been isolated
by distillation and chromatography and spectroscopically characterized.
[C. W. Greengrass, R. Ramage, Tetrahedron 31, 689-694 (1975)].
From ketones 4a, 4b which were present purely or in high concentration or
in mixtures of equilibrium the new cyclic acetales of the formula A are
produced as is known by the reaction with aliphatic 1,2-dioles in acidic
catalysis with separation of water. The separation of water is preferably
realized at boiling point with suitable inert solvents as carriers
(examples 5-10).
If different solvents--toluene, cyclohexane, benzene fractions or
n-pentane--are applied, the epimer ketals are produced in different
proportions (example 5). So from 4a/4b (86:14) in example 2 under the
effect of ethylene glycol in toluene the ketals 5a/5b have been obtained
in the ratio of 3:2. When using n-pentane a ketal mixture 5a/5b was
obtained after even a markedly prolonged reaction period. The ketals of
formula A can be separated alternatively by distillation of the starting
material 4a/4b if need be.
##STR2##
The mixture equilibrated by basic catalysis of ketones 4a/4b (9:91, in
example 3) had to undergo ketalisation reactions as well. Depending on the
solvent used, different mixtures of 5a/5b were obtained, but which
differed from the ketal mixtures 5a/5b obtained from the ketone mixtures
4a/4b (86:14, of example 2) so far as their relative concentrations were
concerned. This varying reaction may be understood as kinetically
controlled reaction during during the ketalisation.
Analogues to the ketals 5a/5b the ketals 6a/6b/6c/6d were obtained by
reaction of 4a/4b with 1,2-propandiol, the ketals 7a/7b/7c/7d with
1,2-butandiol, the ketals 8a/8b/8c/8d with 2,3-butandiol - each of them as
a mixture. The methyl- or ethyl groups of the ketal radical may appear in
an o- or B-configuration.
The compounds 5a, 6a, 6c, 7a, 7c, 8a, 8c are established as
5.beta.-configurated; the compounds 5b, 6b, 6d, 7b, 7d, 8b, 8d as
5.alpha.-configurated. Because starting from (+)-Longifolene the chiral
ketals of the general formula A were obtained by means of the chiral
ketones 4a/4b; 4a/4b exist as a mixture of epimers (5a/5b), respectively
as diastereo isomers. 6a/6b and 7a/7b are constitutionally isomer to
6c/6d, respectively 7c/7d. Starting from (-)Longifolene each of the
enantiomer compounds 5a,b-8a-d are accessable.
Since both the composition of the ketal mixtures depends on the conditions
of the reaction (example 5), and, the single diastereo isomers may be
obtained in purity (examples 6, 7), the proportions within the mixtures
may be adjusted to any level.
The attribution of the structure of the new compounds 5-8 has been based on
the spectroscopical results (examples 5-10). The .sup.1 H-NMR-spectra of
the compounds 5a, 5b (designs 1, 2) have been interpreted in analogy to
the attributions given by C. W. Green-grass and R. Ramage, Tetrahedron 31,
689 (19758) for the ketones 4a, 4b.
The new compounds of the formula A are well suited as odorants due to their
olfactory qualities and their stability. They may be used successfully for
perfume compositions of any fragrance type either as a main component or
in traces to good avail. The examples quoted may not be understood as
limitations.
EXAMPLE 1
Manufacture of Isolongifolene (2)
Over a period of 30 minutes 240 g (0.79 mol) of Longifolene (1) (80% ex
Indian oil of turpentine [.alpha.].sub.D +39.4.degree.) were dropped into
a heated solution (60.degree. C.) of 90 g toluene and 10 g (0.07 mol)
BF.sub.3 -etherate. This was stirred at 100.degree. C. for 3 hours, than
cooled down to room temperature and neutralized. After drying above
Na.sub.2 SO.sub.4 the solvent was distilled at reduced pressure. A raw
product of 198 g (of 70.2% according to GLC) remained.
Gas chromatogram (HP 5890, DBWAX-30 N, 30 m, 150.degree. C.-240.degree. C.,
8.degree. C./min).
EXAMPLE 2
Manufacture of an Isolongifolanene mixture 4a/4b (86:14)
A threeneck-roundbottom-flask with jacketed coil condenser and dropping
funnel was charged with 198 g (0.68 mol) Isolongifolene (2) (70.2%
according to GLC) from example 1 plus 80 g toluene and 68 g (1.48 mol)
formic acid and heated at 60.degree.-70.degree. C. Into this was dropped
over a period of 1 hour 136 g (1.4 mol) H.sub.2 O.sub.2 at 35%
concentration. After stirring for 3 hours at 80.degree.-85.degree. C. it
was cooled to room temperature and worked up. The separated organic phase
was neutralized with sodium carbonate solution and water, dried above
Na.sub.2 SO.sub.4 and the solvent distilled at reduced pressure. 199 g raw
product remained. GLC 4a (71%), 4b (2.5%) [96:4].
Distillation with a 15 cm Vigreux-column produced 165 g raw product of
4a/4b; b.p. 2 mm 120.degree.-153 C. GLC: 4a (74%), 4b (3%).
A subsequent distillation with a column with metallic packing produced: 110
g 4a/4b (74.4% theoretical yield) b.p. 2 mm 137.degree.-141.degree. C.; GC
4a (77%), 4b (12.8%) [86:14].
D 20/4=1,0037
n 20/D=1,5006
[.alpha.]20/D=-8,5.degree.
Gas Chromatogram: Conditions See Example 1
GLC/MS: HP 5970 DBWAX-60 N 60 m 60.degree.-240.degree. C. 4.degree./min 4a
RT=40,47'
MS: m/e (%)=220 (100, M.sup.+), 205 (41), 191 (82), 177 (41), 164 (62), 149
(50), 121 (56), 107 (40), 83 (27), 55 (21), 41 (17). 4b Rt=41,41'
MS: m/e (%)=220 (69, M.sup.+), 205 (23), 191 (55), 177 (44), 164 (100), 149
(55), 121 (53), 107 (37), 91 (21), 55 (21), 41 (19).
EXAMPLE 3
C-3-Epimerization of Isolongifolanone (4a/4b)
880 g (4 mol) raw (undistilled) ketone mixture 4a/4b from example 2 (purity
according to GLC: 4a (63.3%), 4b (2.48%) [96:4]; 750 g methanol, 40 g (0.5
mol) NaOH 50% were charged into a three-neck-roundbottom-flask and stirred
for 8 hours under reflux. After this period 30 g (0.5 mol) concentrated
acetic acid were added to cool down to room temperature. After the
distillation of the solvent at reduced pressure the residual was mixed
with water. The organic phase was then separated. The waterphase was
extracted with 100 ml benzene. The mixed organic phases were washed first
with sodium carbonate solution, then with water and dried above Na.sub.2
SO.sub.4. The solvent was distilled at reduced pressure. 860 g dark brown
oil remained.
GLC: 4a (6.3%), 4b (59.3%) [9:91]
EXAMPLE 4
C-3-Epimerization of pure Isolongifolanone (4a/4b)
440 g (2 mol) purely distilled ketone mixture 4a/4b from example 2 [purity
according to GLC: 4a (77%), 4b (12.8%) [86:14]; 400 ml methanol, 20 g
(0.25 mol) NaOH 50% were charged into a 2 1 three-neck roundbottom-flask
and stirred for 5 hours under reflux. After cooling to room temperature,
15.5 g (0.25 mol) concentrated acetic acid were added; the solvent was
distilled at reduced pressure. The residual was then mixed with water. The
organic phase was separated and the water phase was extracted with 100 ml
benzene. The mixed organic phases were neutralized with sodium carbonate
solution and water; after concentration 430 g brown oil remained.
GLC: 4a (9.2%), 4b (79.5%) [1:9]
Distillation in a 15 cm Vigreux-column produced 411 g 4a/4b (b.p. 2 mm
135.degree.-157.degree. C.). The subsequent distillation in a 40 cm column
with metallic packing produced 399 g (90.7% theor. yield) 4a/4b b.p. 2 mm
139.degree.-142.degree. C.
GLC: 4a (13.4%), 4b (80.6%) [14:86]
D 20/4=1.0042
n 20/D=1.5007
[.alpha.] 20/D=-34.7.degree.
EXAMPLE 5
Reaction of Isolongifolanone 4a/4b with ethylene glycol
220 g (0.6 mol) ketone mixture 4a/4b from example 2, 3 or 4, 186 g (3 mol)
ethylene glycol, 1 g p-toluene sulfonic acid plus 300 ml solvent (toluene,
cyclohexane, benzene (63.degree.-80.degree. C.), n-pentane) were charged
in a 1 l three-neck-roundbottom-flask with water separator and heated at
boiling point for 48-78 hours and stirred with water separation. During
the reaction about 20 ml water each were separated at each stage. After
cooling to room temperature, the mixture was neutralized with sodium
carbonate solution and water, dried above Na.sub.2 SO.sub.4, and the
solvent distilled at reduced pressure 245-265 g raw product of either
yellow or brown oil respectively were obtained.
Distillation with a 15 cm Vigreux-column produced 230 g raw 4a/4b (b.p. 2
mm 68.degree.-170.degree. C.). The subsequent distillation with a 40 cm
column with metallic packing produced about 140 g (53% theor. yield) 5a/5b
of light yellow oil.
Table 1 shows the results in a summary.
TABLE 1
__________________________________________________________________________
Products of the reaction of 4a/4b with ethylenglycol/p-toluenesulfonic
acid
starting material (GLC-%) Reaction
Composition of Product (GLC-%)
a + 4b [4a/4b]
Solvents Temp.
Time
4a 4b 5a 5b [5a/5b]
__________________________________________________________________________
a)
71% 2.5%
[96:4]
Benzene (63-80.degree. C.)
70-72.degree. C.
70 h
7.2
3.8
53.6
2.2
[96:4]
71% 2.5%
[96:4]
Cyclohexane
90-92.degree. C.
48 h
5.1
4.8
51.3
3.8
[93:7]
71% 2.5%
[96:4]
Toluene 120.degree. C.
24 h
1.2
10.4
37.8
19.6
[66:34]
(raw products from example 2)
b)
77% 12.8%
[86:14]
n-Pentane 46-48.degree. C.
84 h
17.1
11.1
60.1
0.8
[99:1]
77% 12.8%
[86:14]
Benzene (63-80.degree.C.)
70-72.degree. C.
72 h
1.8
14.6
57.9
14.3
[80:20]
77% 12.8%
[86:14]
Cyclohexane
90-92.degree. C.
25 h
2.4
10.0
65.5
11.3
[85:14]
77% 12.8%
[86:14]
Toluene 120.degree. C.
25 h
-- -- 84.6
14.3
[86:14]
(Distillate from example 2)
c)
6.3% 59.3%
[9:91]
Benzene (63-80.degree. C.)
70-72.degree. C.
78 h
1.2
14.5
28.6
19.8
[59:41]
6.3% 59.3%
[9:91]
Cyclohexane
90-92.degree. C.
78 h
2.1
11.5
36.9
13.6
[73:27]
6.3% 59.3%
[9:91]
Toluene 120.degree. C.
78 h
2.9
8.4
37.7
13.3
[73:27]
(from example 3)
d)
13.4% 80.6%
[14:86]
Benzene (63-80.degree. C.)
70-72.degree. C.
72 h
-- 22.9
35.6
35.1
[50:50]
13.4% 80.6%
[14:86]
Toluene 120.degree. C.
48 h
1.5
3.3
67.9
19.8
[77:23]
(from example 4)
__________________________________________________________________________
EXAMPLE 6
Manufacture of 5-ethylenedioxy-3.beta.-H-isolongifolane (5a)
20 g purified ketale mixture from example 5b; (purity according to GLC: 5a
(84.6%), 5b (14.3%) [86:14], were distilled once more for purification in
a 1 m spinning band column. 2.8 g 5a as a light yellow oil were obtained,
b.p. 2 mm 142.degree.-143.degree. C.
GLC: 5a (98%), 5b (0,8 ) [99:1]
D 20/4=1,0510
n 20/D=1,5051
GLC/MS: Conditions see example 2
5a RT 42.94'
MS: m/e (%)=264 (23, M.sup.+), 249 (9), 235 (19), 195 (20), 165 (23), 127
(42), 99 (100), 55 (10).
.sup.1 H-NMR: see design 1
.sup.13 C-NMR (CDCl.sub.3), Varian VXR-300): .delta. [ppm]=21.86, 23.39,
26.79, 33.89 (CH.sub.3), 21.06, 25.75, 32.76, 35.89, 37.95, 61.84, 63.71
(CH.sub.2), 48.94, 52.48 (CH), 33.21, 37.67, 56.42, 112.23 (C).
EXAMPLE 7
Isolation of 5-ethylenedioxy-3.alpha.-H-isolongifolane (5b)
1 g of raw ketal mixture from example 5d (purity according to GLC: 5a
(35.6%), 5b (35.1% [1:1]) was purified by repeated (3.times.)
flash-chromatography.
Conditions of Chromatography
150 g silica gel 60, Grain size 0.04-0.063 mm,.(Merck, Art.-No. 9385).
Solvent Benzene/Ethyl acetate=95/5
Weight: 1 g
Yield: 78 mg; GLC: 5a (3%), 5b (90%) [3:97]
GLC/MS: Conditions See Example 2
5b RT 44,67'
MS: m/e (%)=264 (9, M.sup.+), 249 (1), 235 (1), 221 (2), 191 (1), 149 (2),
127 (9), 99 (100), 55 (6), 41 (3).
.sup.1 H-NMR: see design 2
.sup.13 C-NMR (CDCl:), Varian VXR-300): .delta. [ppm]=25.51, 26.72, 26.93,
31.09 (CH.sub.3), 26.01, 30.41, 31.65, 36.90, 37.56, 61.38, 63.05
(CH.sub.2), 49.53, 56.89 (CH), 32.46, 40.99, 56.63, 111.78 (C).
EXAMPLE 8
Manufacture of 5-(1'-Methylethylenedioxy)-isolongifolane 6a/6b/6c/6d
440 g (2 mol) of purified ketone mixture 4a/4b from example 2; (purity
according to GLC: 4a (77%), 4b (12.8%) [86:14], 760 g (10 mol) propylene
glycol-1.2, 600 ml toluene, 2 g p-toluene sulfonic acid were charged into
a 4 l three-neck-roundbottom-flask with water separator. The mixture was
stirred for 30 hours under reflux. After cooling to room temperature it
was neutralized with sodium carbonate solution and water, dried above
Na.sub.2 SO.sub.4 and the solvent was distilled at reduced pressure. 540 g
of light brown raw product remained.
Distillation with a 15 cm Vigreux-column produced 298 g (53.6% theor.
yield) 6a/6b/6c/6d; b.p. 2 mm 158.degree.-162.degree. C.).
GLC/MS: Conditions See Example 2
RT 41.11'
MS: m/e (%)=278 (21, M.sup.+), 263 (19), 249 (40), 179 (41), 141 (39), 113
(100), 83 (20), 55 (31).
RT 42,03'
MS: m/e (%)=278 (29, M.sup.+), 263 (22), 249 (55), 209 (40), 179 (49), 141
(42), 113 (100), 83 (21), 55 (31).
RT 42,11'
MS: m/e (%)=278 (23, M.sup.+), 263 (21), 249 (44), 209 (35), 179 (47), 141
(39), 113 (100), 83 (21), 55 (34).
Rt 42,47'
MS: m/e (%)=278 (29, M.sup.+), 263 (21), 249 (51), 209 (37), 179 (47), 141
(44), 113 (100), 83 (21), 55 (26).
EXAMPLE 9
Manufacture of 5-(1'-Ethyl-ethylenedioxy)-isolongifolane 7a/7b/7c/7d
220 g (1 mol) purified ketone mixture 4a/4b from example 2 (purity
according to GLC: 4a (77%), 4b (12.8%) [86:15], 270 g (3 mol)
1,2-butandiol, 300 ml cyclohexane, and 1 g p-toluene sulfonic acid were
charged into a 1 l three-neck-roundbottom-flask with water separator. The
mixture was stirred for 50 hours. After cooling to room temperature it was
then neutralized with sodium carbonate solution and water and dried above
Na.sub.2 SO.sub.4. After distillation of the solvent at reduced pressure
328 g of light brown oil remained.
A subsequent distillation with a 15 cm Vigreux-column produced 195 g (66.8%
theor. yield) 7a/7b/7c/7d; b.p. 2 mm 152.degree.-157.degree. C. as light
yellow oil.
GLC/MS: Conditions See Example 2
Rt 42,55'
MS: m/e (%)=292 (16, M.sup.+), 277 (15), 263 (37), 223 (27), 193 (28),155
(26), 127 (100), 83 (13), 55 (43).
Rt 43,37'
MS: m/e (%)=292 (32, M.sup.+), 277 (25), 263 (56), 223 (48), 193 (41), 155
(37), 127 (100), 83 (17), 55 (49).
Rt 43,66'
MS: m/e (%)=292 (19, M.sup.+), 277 (19), 263 (42), 223 (45), 193 (34), 155
(28), 127 (100), 83 (13), 55 (50).
Rt 44,29'
MS: m/e (%)=292 (32, M.sup.+), 277 (24), 263 (57), 223 (43), 193 (41), 155
(43), 127 (100), 83 (17), 55 (50).
EXAMPLE 10
Manufacture of 5-(1',2'-dimethyl-ethylene dioxy)-isolongifolane 8a/8b/8c/8d
220 g (1 mol) of purified ketone mixture 4a/4b from example 2 (purity
according to GLC: 4a (77%), 4b (12.8%) [86:14]; 270 g (3 mol)
2,3-butandiol, 300 ml cyclohexane, and 1 g p-toluene sulfonic acid were
charged into a 1 l three-neck-roundbottom-flask and stirred for 50 hours
under reflux. After cooling to room temperature it has been neutralized
with sodium carbonate solution and water and dried above Na.sub.2
SO.sub.4. The solvent was distilled at reduced pressure. 275 g light brown
raw product remained.
Distillation with a 15 cm Vigreux-column produced 211 g (72.2% theor.
yield) 8a/8b/8c/8d; b.p. 2.5 mm 158.degree.-162.degree. C. as a light
yellow oil.
D 20/4=1,0115
n 20/D=1,4975
GLC/MS: Conditions see example 2
Rt 39,69'
MS: m/e (%)=292 (41, M.sup.+), 277 (25), 263 (57), 223 (50), 193 (49), 155
(50), 127 (100), 83 (20), 55 (29).
Rt 40,14'
MS: m/e (%)=292 (47, M.sup.+), 277 (30), 263 (63), 223 (59), 193 (53), 155
(51), 127 (100), 83 (20), 55 (35).
Rt 42,76'
MS: m/e (%)=292 (16, M.sup.+), 277 (14), 263 (28), 223 (28), 193 (26), 155
(25), 127 (100), 83 (15), 55 (28).
Rt 43,36'
MS: m/e (%)=292 (56, M.sup.+), 277 (40), 263 (91), 223 (78), 193 (66), 155
(64), 127 (100), 83 (38), 55 (41).
EXAMPLE 11
Description of Odours of Ketals 5 to 8
The olfactory qualities of the materials at 10% in Ethanol have been
evaluated by a group of experts using smelling strips. Their findings were
as follows:
5a/5b [86:14] from example 5b:
strong, sweet-woody, with a velvety-ambra accent and flowery aspects.
5a from example 6:
strongly woody with a mossy ambra-accent and a fresh effect.
5b from example 7:
woody, light flowery, with a softly earthy ambra note, a bit weaker than
compound 5a.
6a/6b/6c/6d (from example 8):
strongly woody, powdery, with a fresh ambra accent.
7a/7b/7c/7d (from example 9):
dry, woody
8a/8b/8c/8d (from example 10):
strongly woody, with aspects of mossy, earthy and sweet-animal notes.
The odors of all compounds were found to be extremely longlasting and could
be smelled after several weeks.
EXAMPLE 12
Perfume Base of a Flowery-woody Type
______________________________________
Oil of bergamot 7.5
Linalool 4.0
Phenyl ethyl alcohol 5.0
Benzyl acetate 2.0
Citronellol 2.0
Hedione .RTM. (a) 10.0
Lyral .RTM. (b) 4.0
Hydroxycitronellal 2.5
Roseoxide 1 (c) 10% in DPG
2.5
Hexyl cinnamic aldehyde, alpha
7.5
Patchouly Oil Indonesian
4.0
Iso-E-Super .RTM. (b) 2.0
Vetiveryl acetate 2.0
Brahmanol .RTM. F (c) 2.0
Benzcylsalicylat 2.0
cis-3-Hexenylsalicylat
1.0
Cedramber .RTM. (b) 1.0
Musk Xylene 1.0
Indole 10% in DPG 0.5
Extract of Opoponax 0.5
Extract of Oakmoss 50% in DPG
5.0
68.0
______________________________________
(a) Firmenich
(b) IFF
(c) DRAGOCO
The perfume base of the indicated formula presents a well balanced
flowery-woody character which may be markedly amplified and harmonized by
addition of 32 parts of 5a/5b (80:20).
EXAMPLE 13
Perfume Base of the Fougere Type
______________________________________
Oil of bergamot 18.0
Oil of Lavandin Super 15.0
Lilial .RTM. 10.0
p-anisaldehyde 3.0
Coumarin 5.0
Hexyl cinnamic aldehyde, alpha
20.0
Ambrinol epoxide 10% in DPG
0.5
Ambroxan .RTM. (d) 10% in DPG
1.0
Romaryl .RTM. (c) 10.0
Peppermint oil 1.0
82.5
______________________________________
(c) DRAGOCO
(d) Henkel
The perfume base of the indicated formula shows a fresh herbal fougere
odor. An addition of 7.5 parts 6a/6b/6c/6d smoothes the composition and
puts an accent on the ambra-woody note. Alternatively, an addition of 7.5
parts 8a/8b/8c/8d also smoothes the composition but puts the accent on an
animal woody aspect.
EXAMPLE 14
______________________________________
Oil of Galbanum ED 0.5
Eugenol 1.0
Methylionone-gamma 5.0
cis-3-Hexenylsalicylat
6.0
Benzyl acetate 8.0
Lignofix .RTM. (c) 5.0
Hedione .RTM. (a) 10.0
Bencylsalicylat 10.0
Hexyl cinnamic aldehyde, alpha
12.0
Phenyl ethyl alcohol 15.0
72.5
______________________________________
(a) Firmenich
(c) DRAGOCO
The perfume oil of the indicated formula shows a harmonic flowery green
character. Alternative addition of either 7.5 parts 5a/5b or 7a/7b/7c/7d
produces a very desirable balancing in a very natural effect.
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